EP0955092B1 - Catalyseur à base de zeolithe y non globalement désaluminée, de bore et/ou de silicium et procédé d'hydrocraquage - Google Patents

Catalyseur à base de zeolithe y non globalement désaluminée, de bore et/ou de silicium et procédé d'hydrocraquage Download PDF

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EP0955092B1
EP0955092B1 EP99400974A EP99400974A EP0955092B1 EP 0955092 B1 EP0955092 B1 EP 0955092B1 EP 99400974 A EP99400974 A EP 99400974A EP 99400974 A EP99400974 A EP 99400974A EP 0955092 B1 EP0955092 B1 EP 0955092B1
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catalyst
weight
zeolite
mpa
group
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EP0955092A1 (fr
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Nathalie George-Marchal
Samuel Mignard
Slavik Kasztelan
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IFP Energies Nouvelles IFPEN
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite

Definitions

  • the hydrogenating function is provided either by one or more metals of the Group VIII of the Periodic Table of Elements, such as Iron, Cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, either by a combination of minus a group VIB metal of the periodic table such as chromium, molybdenum and tungsten and at least one group VIII metal, preferably non-noble.
  • metals of the Group VIII of the Periodic Table of Elements such as Iron, Cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, either by a combination of minus a group VIB metal of the periodic table such as chromium, molybdenum and tungsten and at least one group VIII metal, preferably non-noble.
  • Low acidity supports generally consist of amorphous oxides or poorly crystallized. In low acid carriers, there is the family of silica-aluminas amorphous. Some catalysts of the hydrocracking market consist of silica-alumina associated with a group VIB and VIII metal sulfide combination. These Catalysts make it possible to treat fillers with poison contents heteroatomic, sulfur and nitrogen, elevated. These catalysts have a very good selectivity in middle distillates, they are very resistant to high nitrogen content and the products formed are of good quality. The disadvantage of these catalyst systems based on support amorphous is their weak activity.
  • the Applicant has discovered that to obtain a hydrocracking catalyst having a good level of activity and good stability on loads with a high nitrogen content, it is advantageous to associate an acidic amorphous oxide matrix of doped alumina type by boron and silicon, and possibly by phosphorus and possibly at least one element of group VIIA and in particular fluorine at a zeolite Y not dealuminated globally very acidic and at least one element Group VIIB.
  • zeolite not dealuminated globally a zeolite Y of faujasite structure (Zeolite Molecular Sieves Structure, Chemistry and Uses, D. W. BRECK, J. WILLEY and Sons 1973).
  • the crystalline parameter of this zeolite may have decreased by extraction of aluminum from the structure or framework during the preparation but the Global Si02 / A1203 ratio did not change because aluminum was not extracted chemically zeolite crystals.
  • the zeolite crystals therefore contain aluminum extracted from the framework in the form of extra-lattice aluminum.
  • Such a zeolite not dealuminally globally therefore has a silicon and aluminum composition expressed by the overall SiO2 / Al2O3 ratio equivalent to the dealuminated Y zeolite of departure.
  • This zeolite Y not dealuminated globally can be in the hydrogen form be at least partially exchanged with metal cations, for example at using alkaline earth metal cations and / or rare earth metal cations of atomic number
  • the catalysts obtained by the present invention are shaped into the form of grains of different shapes and sizes. They are used in general in the form cylindrical or multi-lobed extrusions such as bilobed, trilobed, poly-lobed form straight or twisted, but can eventually be manufactured and used under the crushed powder form, tablets, rings, balls, wheels. They present a specific surface area measured by nitrogen adsorption according to the BET method (Brunauer, Emmett, Teller, J. Am. Chem. Soc., Vol. 60, 309-316 (1938)) greater than 140 m 2 / g, one porous volume measured by mercury porosimetry between 0.2 and 1.5 cm3 / g and a pore size distribution that can be monomodal, bimodal or polymodal. Preferably, the catalysts of the present invention have a distribution of monomodal pores.
  • Said catalyst has an activity in hydrocracking of gas oil cuts under void more important than the catalytic formulas known in the prior art. Without want to be bound by any theory, it seems that this activity particularly
  • the catalysts of the present invention are due, on the one hand, to the acidity of the catalyst by the presence of an acidified alumina matrix by the addition of boron and / or silicon, which also induces an improvement of the properties hydrodéazotante of the active phase comprising at least one metal of group VIB and possibly at least one Group VIII metal and secondly by the presence of the highly acidic Y zeolite, a good part of the acidity of which will be neutralized by the compounds nitrogenous but whose acid sites remaining under the operating conditions will give a sufficient hydrocracking activity to the catalyst.
  • the catalyst of the present invention can be prepared by any of the methods well known to those skilled in the art.
  • It can be introduced by one or more impregnation operations of the shaped and calcined support, by a solution of precursors of group VIII metal oxides (in particular cobalt and nickel) when the precursors of the oxides of Group VIB metals (in particular molybdenum or tungsten) were previously introduced at the time of mixing of the support. It can finally be introduced by one or more impregnation operations of the support calcined consisting of zeolite and alumina matrix optionally doped with B, Si, P and / or F, by solutions containing the precursors of the metal oxides of the groups VIB and / or VIII. the precursors of the Group VIII metal oxides being preferably introduced after those in Group VIB or at the same time as those.
  • a step of intermediate calcination of the catalyst should be carried out at a temperature of between 250 and 600 ° C.
  • Group VIII element sources that can be used are well known from the skilled person. For example, we will use nitrates, sulphates, halides.
  • Group VIIB element sources that can be used are well known the skilled person. Ammonium salts, nitrates and chlorides.
  • a preferred method according to the invention consists of prepare an aqueous solution of at least one group VIB element and optionally of at least one Group VIII element and a phosphorus compound and to proceed a so-called dry impregnation, in which the pore volume of the precursor is filled by the solution containing the group VIB metal, possibly the metal of the group VIII, phosphorus and possibly the element of group VIIA.
  • the phosphorus and the element chosen from the group VIIA halide ions may be introduced by one or more impregnation operations with excess of solution on the calcined precursor.
  • the preferred phosphorus source is orthophosphoric acid H 3 PO 4, but its salts and esters such as ammonium phosphates are also suitable. Phosphomolybdic acid and its salts, phosphotungstic acid and its salts can also be advantageously employed.
  • the phosphorus may for example be introduced in the form of a mixture of phosphoric acid and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinolines and compounds of the pyrrole family.
  • Phosphorus (P), B and the element chosen from the group VIIA halide ions can be introduced separately by one or more impregnation operations with excess of solution on the calcined precursor.
  • Group VIIA element sources that can be used are well known the skilled person.
  • fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound. In the latter case, the salt is advantageously formed in the reaction mixture by reaction between the organic compound and the acid hydrofluoric.
  • hydrolysable compounds which can release fluoride anions in the water, such as ammonium fluorosilicate (NH4) 2SiF6, silicon tetrafluoride SiF4 or sodium Na2SiF6.
  • Fluoride can be introduced for example by impregnation with an aqueous solution of hydrofluoric acid or of ammonium fluoride.
  • Hydrocracking conditions such as temperature, pressure, recycling rate of hydrogen, hourly volumetric velocity, may be very variable depending on the nature of the load, the quality of the desired products and the facilities available to the refiner.
  • the temperature is generally above 200 ° C and often between 250 ° C and 480 ° C.
  • the pressure is greater than 0.1 MPa and often greater than 1 MPa.
  • the hydrogen recycling rate is at least 50 and often between 80 and 5000 normal liters of hydrogen per liter of charge.
  • the hourly space velocity is generally between 0.1 and 20 volume of filler per volume of catalyst and hour.
  • the catalysts of the present invention are preferably subjected to sulphurization to transform, at least in part, the metallic species into sulphide before they come into contact with the charge to be treated.
  • This activation treatment by sulfuration is well known to those skilled in the art and can be carried out by any method already described in the literature.
  • a conventional sulfurization method well known to those skilled in the art consists of to heat in the presence of hydrogen sulphide at a temperature between 150 and 800 ° C, preferably between 250 and 600 ° C, generally in a bed reaction zone through.
  • the catalyst can be used under varying hydrocracking conditions with pressures of at least 2 MPa, a reaction temperature of at least 230 ° C, a ratio of H2 / charge of at least 100 NI H2 / l of charge and a volume hourly velocity of 0.1-10h-1.
  • the treated hydrocarbon feedstocks have initial boiling points of at least 150.degree. preferably at least 350 ° C, and more preferably it is a hot cup between 350-580 ° C.
  • the catalyst of the present invention can be used for the hydrocracking of various hydrocarbon cuts, for example vacuum distillate type cuts heavily loaded with sulfur and nitrogen. In a first partial hydrocracking mode the conversion level is less than 55%.
  • the catalyst according to the invention is then used at a temperature generally greater than or equal to 230 ° C or 300 ° C, generally at most 480 ° C, and often between 350 ° C and 450 ° C.
  • Pressure is generally greater than 2 MPa and less than or equal to 12 MPa.
  • a pressure range moderate is particularly interesting, which is 7.5-11 MPa, preferably 7.5-10 MPa or 8-11MPa and advantageously 8.5-10 MPa.
  • the hydrotreatment function is provided by at least one metal or group VIII metal compound such as nickel and cobalt especially.
  • a combination of at least one metal or metal compound can be used group VIB (in particular molybdenum or tungsten) and at least one metal or Group VIII metal compound (in particular cobalt or nickel) of the classification periodic elements.
  • the total concentration of Group VIB metal oxides and VIII is between 5 and 40% by weight and preferably between 7 and 30% by weight and the weight ratio expressed as metal oxide to metal (or metals) of group VIB metal (or metals) group VIII is between 1.25 and 20 and preferably between 2 and 10.
  • this catalyst may contain phosphorus.
  • the first stage generally takes place at a temperature of 350-460 ° C, preferably 360-450 ° C, a total pressure of 2 to 12 MPa; and preferably 7.5-11 MPa, 7.5-10 MPa or 8-11 MPa or 8.5-10 MPa, an hourly volume velocity of 0.1-5h-1 and preferably 0.2-2h-1 and with an amount of hydrogen of at least 100N1 / N1 charge, and preferably 260-3000N1 / N1 charge.
  • the catalysts of the present invention exhibit better activity in conversion, hydrodesulfurization, hydrodenitrogenation and better selectivity in middle distillates as commercial catalysts.
  • the life of the catalysts is improved in the moderate pressure range.
  • the catalyst of the present invention can be used for hydrocracking under high hydrogen pressure conditions from minus 8.5 MPa, preferably at least 9 MPa or at least 10 MPa.
  • Treated sections are for example vacuum distillate type highly charged with sulfur and nitrogen which have previously hydrotreated.
  • the conversion level is greater than or equal to 55%.
  • the oil cutting conversion process proceeds in two stages, the catalyst according to the invention being used in the second step.
  • the total concentration of Group VIB and VIII metal oxides is between and 40% by weight and preferably between 7 and 30% by weight and the weight ratio expressed metal oxide (or metals) group VIB on metal (or metals) of the group VIII is between 1.25 and 20 and preferably between 2 and 10.
  • this catalyst may contain phosphorus.
  • the temperatures are generally greater than or equal to 230 ° C and often between 300 ° C and 430 ° C.
  • the pressure is generally greater than 8.5 MPa and preferably greater than 10 MPa.
  • the quantity of hydrogen is at least 100 l / l of charge and often between 200 and 3000 l / l of hydrogen per liter of filler.
  • Speed hourly volume is usually between 0.15 and 10h-1.
  • the catalysts of the present invention exhibit better activity in conversion and better selectivity in middle distillates than catalysts even for zeolite contents considerably lower than those commercial catalysts.
  • a hydrocracking catalyst support containing a zeolite Y not globally dealuminated was manufactured in large quantities so as to prepare different catalysts based on the same support. For this purpose, 19.7% by weight of a zeolite Y is used. dealuminated crystal parameter equal to 2.453 nm and overall SiO2 / Al2O3 ratio 6.6 and SiO2 / Al2O3 ratio of frame 8.6, which is mixed at 80.3% by weight a matrix composed of ultrafine tabular boehmite or marketed alumina gel under the name SB3 by Condisputeda Chemie Gmbh.
  • This powder mix has been then mixed with an aqueous solution containing 66% nitric acid (7% by weight of acid per gram of dry gel) and then kneaded for 15 minutes. At the end of this mixing, the paste obtained is passed through a die having cylindrical orifices of diameter equal to 1.4 mm. The extrudates are then dried overnight at 120 ° C. and then calcined at 550 ° C for 2 hours in moist air containing 7.5% water volume. We obtain cylindrical extrudates 1.2 mm in diameter having a surface area of 351 mm. m2 / g, a pore volume of 0.58 cm3 / g and a monomodal pore size distribution centered on 10 nm.
  • the analysis of the matrix by X-ray diffraction reveals that it is composed of cubic gamma alumina of low crystallinity and zeolite Y of 2.44 nm mesh parameter and overall SiO2 / Al2O3 ratio of 6.7 and ratio SiO2 / Al2O3 framing 13.9.
  • Support extrudates containing a non-dealuminated parameter Y zeolite crystalline at 2.444 nm and overall SiO2 / Al2O3 ratio of 6.7 and SiO2 / Al2O3 ratio 13.9 of Example 1 are impregnated dry with an aqueous solution of a mixture of ammonium heptamolybdate and nickel nitrate, dried overnight at 120 ° C under air and finally calcined under air at 550 ° C.
  • the weight contents in oxides of the CZ3 catalyst obtained are shown in Table 1.
  • the final catalyst CZ3 contains in particular 16.6% by weight of Y zeolite.
  • Catalyst CZ3 was then impregnated with an aqueous solution containing ammonium biborate. After maturation at room temperature in an atmosphere saturated with water, the impregnated extrusions are dried overnight at 120.degree. calcined at 550 ° C for 2 hours in dry air.
  • a catalyst named CZ3B is obtained: NiMo / alumina-Y doped with boron.
  • a catalyst CZ3Si is prepared by impregnating the CZ3 catalyst with a Rhodorsil EP1 silicone emulsion (Rhone-Poulenc). The impregnated extrudates are then dried overnight at 120 ° C. then calcined at 550 ° C for 2 hours in dry air.
  • a catalyst CZ3PSi was obtained by the same procedure as the catalyst CZ3PB above but replacing in the impregnation solution the boron precursor by the Rhodorsil EP1 silicone emulsion (Rhone-Poulenc). Finally, a catalyst CZ3PBSi was obtained impregnation of the CZ3P catalyst with an aqueous solution containing the ammonium biborate and the Rhodorsil EP1 silicone emulsion (Rhone-Poulenc). The other steps of the procedure are the same as those indicated above.
  • the characteristics of CZ3 catalysts are summarized in Table 1.
  • a hydrocracking catalyst support containing a small amount of zeolite Y not globally dealuminated has been manufactured in large quantities so as to be able to prepare different catalysts based on the same support.
  • 8.6% weight a non-dealuminated Y zeolite with a crystalline parameter equal to 2.453 nm and a ratio SiO2 / Al2O3 overall of 6.6 and SiO2 / Al2O3 ratio of frame 8.6, which is 91.4% weight mixture of a matrix composed of ultrafine tabular boehmite or gel alumina marketed under the name SB3 by Condéa Chemie Gmbh.
  • This mixture of powder was then mixed with an aqueous solution containing the acid 66% nitric acid (7% by weight of acid per gram of dry gel) then kneaded during 15 minutes.
  • the paste obtained is passed through a die having cylindrical orifices with a diameter of 1.4 mm.
  • the extrusions are then dried overnight at 120 ° C and calcined at 550 ° C for 2 hours in moist air containing 7.5% water volume. Cylindrical extrusions of 1.2 mm are thus obtained. diameter, having a surface area of 259 m 2 / g, a pore volume of 0.57 cm 3 / g and a monomodal pore size distribution centered on 10 nm.
  • the analysis of the matrix by X-ray diffraction reveals that it is composed of cubic gamma alumina of low crystallinity and zeolite Y of 2,444 nm mesh and ratio parameter SiO2 / Al2O3 overall 6.7 and SiO2 / Al2O3 ratio of 14.1 framing.
  • Support extrudates containing a small amount of zeolite Y not dealuminated with crystalline parameter equal to 2.444 nm and overall SiO2 / Al2O3 ratio of 6.7 and ratio SiO 2 / Al 2 O 3 of 14.1 of Example 3 are dry impregnated with a solution aqueous solution of a mixture of ammonium heptamolybdate and nickel nitrate, dried overnight at 120 ° C under air and finally calcined under air at 550 ° C.
  • the weight contents in oxides CZ5 catalyst obtained are shown in Table 2.
  • the final catalyst CZ5 in particular contains 7.1% by weight of zeolite Y of 2,443nm mesh parameter and overall SiO2 / Al2O3 ratio of 6.8 and SiO2 / Al2O3 framework ratio of 14.9.
  • the catalyst CZ5 was then impregnated with an aqueous solution containing ammonium biborate. After maturation at room temperature in an atmosphere saturated with water, the impregnated extrusions are dried overnight at 120.degree. calcined at 550 ° C for 2 hours in dry air.
  • a catalyst named CZ5B is obtained.
  • a catalyst CZ5Si was prepared by impregnation of the catalyst CZ5 with a Rhodorsil EP1 silicone emulsion (Rhone-Poulenc). Extruded impregnated are then dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours. hours in dry air.
  • a catalyst CZSBSi was obtained impregnation of CZ5 catalyst with an aqueous solution containing ammonium biborate and the Rhodorsil EP1 silicone emulsion (Rhone-Poulenc).
  • the impregnated extrusions are then dried overnight at 120 ° C and then calcined at 550 ° C for 2 hours in air dry.
  • the support extrudates containing a zeolite Y of Example 3 are also dry impregnated with an aqueous solution of a mixture of ammonium heptamolybdate, of nickel nitrate and orthophosphoric acid, dried overnight at 120 ° C. in air and finally calcined in air at 550 ° C.
  • the weight contents in oxides of the catalyst CZ5P obtained are shown in Table 2.
  • This powder mixture was then mixed with an aqueous solution containing 66% nitric acid (7% by weight of acid per gram of dry gel) and then kneaded for 15 minutes. At the end of this mixing, the paste obtained is passed through a die having cylindrical orifices of diameter equal to 1.4 mm.
  • the extrudates are then dried overnight at 120 ° C. and then calcined at 550 ° C for 2 hours in moist air containing 7.5% water volume.
  • cylindrical extrudates 1.2 mm in diameter having a specific surface area of 365 m2 / g, a pore volume of 0.53 cm3 / g and a pore size distribution monomodal centered on 11 nm.
  • Support extrudates containing silica-alumina and non-dealuminated Y zeolite crystalline parameter equal to 2.444 nm and overall SiO2 / Al2O3 ratio of 6.8 and SiO 2 / Al 2 O 3 ratio of 14.7 in Example 5 are dry impregnated with aqueous solution of a mixture of ammonium heptamolybdate and nickel nitrate, dried overnight at 120 ° C under air and finally calcined in air at 550 ° C.
  • the contents weightings of the catalyst CZ17 obtained are shown in Table 1.
  • Final CZ17 catalyst contains in particular 16.3% by weight of zeolite Y.
  • Catalyst CZ17 was then impregnated with an aqueous solution containing ammonium biborate. After maturation at room temperature in an atmosphere saturated with water, the impregnated extrusions are dried overnight at 120.degree. calcined at 550 ° C for 2 hours in dry air. We get a named catalyst CZ17B.
  • Example 7 Comparison of Hydrocracking Catalysts of a Vacuum Diesel Fuel at low pressure.
  • the catalysts whose preparations are described in the preceding examples are used under the conditions of hydrocracking at moderate pressure on a petroleum feedstock whose main characteristics are as follows: initial point 365 ° C point 10% 430 ° C point 50% 472 ° C 90% point 504 ° C period 539 ° C pour point + 39 ° C density (20/4) 0.921 Sulfur (% wt) 2.46 Nitrogen (ppm weight) 1130
  • the catalytic test unit comprises two reactors in a fixed bed, with upward flow of the charge ("up-flow"). In each of the reactors, 40 ml of catalyst are introduced.
  • the first hydrotreatment catalyst HTH548 sold by Procatalyse comprising a group VIB element and a group VIII element deposited on alumina.
  • the second reactor the one in which the feed passes last, is introduced the hydrocracking catalyst (CZ5 series). Both catalysts undergo an in situ sulphurization step prior to reaction. It should be noted that any in situ or ex situ sulphurization method is suitable. Once the sulfurization is complete, the charge described above can be transformed. The total pressure is 8.5 MPa, the hydrogen flow rate is 500 liters of hydrogen gas per liter of injected charge, the hourly volume velocity is 0.8 h -1. Both reactors operate at the same temperature.
  • the catalytic performances are expressed by the gross conversion at 400 ° C. (CB), by gross selectivity to middle distillates (150-380 ° C cut) (SB) and by conversion to hydrodesulfurization (HDS) and hydrodenitrogenation (HDN). These catalytic performances are measured on the catalyst after a stabilization period, usually at less 48 hours, has been respected.
  • the catalytic test unit consists of two fixed bed reactors with upflow of the charge ("up-flow"). In each of the reactors, 40 ml of catalyst are introduced. In the first reactor, the one in which the feed passes first, the Hydrotreating first stage catalyst HR360 sold by the company Procatalyse comprising a Group VIB element and a Group VIII element deposited on alumina. In the second reactor, the one in which the charge passes last, introduces the second stage catalyst, that is to say the hydroconversion catalyst (CZ5 series). Both catalysts undergo an in situ sulphurization step before reaction. It should be noted that any in situ or ex situ sulphurization method is suitable. A Once the sulphurization has been carried out, the charge described above can be transformed. Pressure total is 12 MPa, the hydrogen flow rate is 1000 liters of hydrogen gas per liter injected charge, the hourly volume velocity is 0.9h-1.
  • the catalytic performances are expressed by the temperature which makes it possible to reach a gross conversion level of 70% and the average gross distillate selectivity (cut 150 ° C-380 ° C). These catalytic performances are measured on the catalyst after a period of stabilization, generally at least 48 hours, has been respected.
  • the reaction temperature is set so as to reach a gross conversion CB equal to 70% by weight.
  • Table 7 we have reported the reaction temperature and the crude selectivity for the catalysts of the CZ5 series.

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EP99400974A 1998-05-06 1999-04-21 Catalyseur à base de zeolithe y non globalement désaluminée, de bore et/ou de silicium et procédé d'hydrocraquage Expired - Lifetime EP0955092B1 (fr)

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FR9805735A FR2778343B1 (fr) 1998-05-06 1998-05-06 Catalyseur a base de zeolithe y non globalement desaluminee, de bore et/ou de silicium et procede d'hydrocraquage
FR9805735 1998-05-06

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DE (1) DE69925781T2 (https=)
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FR2778343B1 (fr) * 1998-05-06 2000-06-16 Inst Francais Du Petrole Catalyseur a base de zeolithe y non globalement desaluminee, de bore et/ou de silicium et procede d'hydrocraquage
US7462338B2 (en) * 2004-12-28 2008-12-09 Umicore Ag & Co. Kg Boron-alumina catalyst support
US20070125684A1 (en) * 2005-09-14 2007-06-07 Biesmans Martijn H Hydrocracking Catalyst and Process
CN102438745A (zh) 2009-04-21 2012-05-02 阿尔比马尔欧洲有限公司 含有磷和硼的氢化处理催化剂
FR2952379B1 (fr) * 2009-11-10 2012-05-11 Inst Francais Du Petrole Procede d'hydrocraquage mettant en oeuvre une zeolithe modifiee par un traitement basique
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DE69925781T2 (de) 2005-11-03
KR19990088061A (ko) 1999-12-27
KR100589019B1 (ko) 2006-06-13
US20020016253A1 (en) 2002-02-07
DE69925781D1 (de) 2005-07-21
US20020033355A1 (en) 2002-03-21
EP0955092A1 (fr) 1999-11-10
JP2000024509A (ja) 2000-01-25
ES2245079T3 (es) 2005-12-16
FR2778343B1 (fr) 2000-06-16
FR2778343A1 (fr) 1999-11-12
JP4547564B2 (ja) 2010-09-22
US6719895B2 (en) 2004-04-13
US6420296B2 (en) 2002-07-16

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